JPH07709B2 - Thermally stabilized chlorine-containing resin composition - Google Patents

Abstract

A thermally stabilized chlorine-containing resin composition comprising a chlorine-containing resin and a stabilizer consisting essentially of (a) an over based alkaline earth metal carboxylate or phenolate complex, (b) zeolite, (c) calcium hydroxide and (d) a complex of at least one metal perchlorate selected from the group consisting of sodium, magnesium, calcium and barium perchlorates with at least one compound selected from the group consisting of polyhydric alcohols and their derivatives. The stabilizer consisting essentially of the above four components (a) to (d) exhibits excellent effects in the prevention of the discoloration and the deterioration in physical properties of the chlorine-containing resin, both accompanying the thermal degradation caused when the resin is subjected to thermoforming, particularly powder molding or exposed to a high temperature atmosphere for a long period of time.

Description

TECHNICAL FIELD The present invention relates to a heat-stabilized chlorine-containing resin composition.
More specifically, it is formed by combining a chlorine-containing resin with an overbased alkaline earth metal salt, zeolite and calcium hydroxide, and a complex of a metal salt of perchloric acid and a polyhydric alcohol or a derivative thereof. The present invention relates to a chlorine-containing resin composition having an excellent effect of preventing thermal deterioration and coloration during processing and when exposed to a high temperature atmosphere for a long time.

(Prior Art) Chlorine-containing resin compositions are affected by heat during thermoforming, and molded articles after processing are colored and decomposed by dehydrochlorination when exposed to high temperature for a long time. (Or) There is a drawback that the physical properties are deteriorated and the commercial value of the molded product is remarkably reduced. Therefore, it is already known to stabilize a chlorine-containing resin composition with a stabilizer in which a metal carboxylate such as barium-zinc and an organic phosphite, a phenolic antioxidant are combined with a chlorine-containing resin. .

Molded articles made of this chlorine-containing resin composition have been frequently used as interior parts for automobiles in recent years, and especially molded articles made of a soft compound are used to improve impact resilience, texture and stability together with the purpose of weight reduction. The molded parts for interior are made by injecting or joining urethane inside or on the back of the product and foaming. Conventionally, a molded part for such an automobile interior has been conventionally formed into a sheet by calendering or extrusion, and then subjected to vacuum forming to obtain the interior molded part. Therefore, the processing conditions at the time of thermoforming are almost the same as those of general molded articles, and the chlorine-containing resin composition to be used for the thermosetting was sufficiently stabilized by the combination of the above-mentioned known stabilizers. However, it is difficult to give a complicated leather grain pattern to the surface skin of this molded product, and the texture is not sufficient, so this improvement has been desired.

Against this background, a powder molding method has been adopted and carried out in recent years as the improved method, and as this molding method, for example, JP-A-60-161451, the same, 61-
No. 91238, No. 62-270645, No. 63-125553, No. 63-132953, No. 64-65157 and U.S. Pat. ing. According to these prior arts, a stabilizer, a plasticizer, a pigment, etc. are added to a chlorine-containing resin, blended, sufficiently heated and mixed, so-called drive blending is performed to obtain a powdery resin composition. The powdery resin composition is sprayed in a mold at a high temperature of 200 to 280 ° C. by a powder rotation molding method or a powder slush molding method, melted, welded, and cooled. There is. The molded parts for automobile interiors obtained by such powder molding have advantages such that the skin is precise and has a complex and heavy leather-like pattern and texture. However, this powder molding process is a method in which a powdery chlorine-containing resin composition is dispersed and melted and welded in a high temperature mold without passing through a step such as kneading-gelling.
The chlorine-containing resin has a drawback that the resin composition easily causes thermal decomposition accompanied by coloring depending on the component and the addition amount of the conventionally known heat stabilizer. There is also a problem that the phenomenon of mold contamination occurs on the mold surface due to the continuous powder molding process. Furthermore, as a secondary processed product, after thermoforming, it is integrated with urethane to make interior parts. However, there is a drawback in that such molded parts are colored when exposed at a high temperature of 80 to 130 ° C. for 300 hours or more, resulting in deterioration of quality.

In order to deal with such a molding method different from conventional methods and severe heat conditions, heat stabilization methods using various stabilizers have been proposed so far, but they are not yet sufficient, and this improvement is desired. It is rare.

(Problems to be Solved by the Invention) When thermoforming a chlorine-containing resin composition, the present invention provides thermal stabilization under severe heat conditions such as powder molding, and integral molding of the resin composition and urethane. Chlorine-containing resin heat-stabilized with a stabilizer that has excellent effects on technical issues such as preventing coloration when exposed to high temperature for a long time and preventing mold contamination. It is intended to obtain a composition.

(Means for Solving the Problems) That is, the present invention provides a chlorine-containing resin with a stabilizer (a)
An alkaline earth metal overbased carboxylate or phenolate complex, (b) zeolite and calcium hydroxide, and (c) sodium perchlorate, magnesium,
A heat-stabilized chlorine-containing resin composition obtained by adding a calcium salt or barium salt and at least one complex of a polyhydric alcohol or a derivative thereof in combination.

Hereinafter, the present invention will be described in more detail.

The stabilizer component (a) complex constituting the composition of the present invention comprises an excess equivalent amount of an alkaline earth metal oxide or hydroxide,
It can be easily produced by reacting an organic carboxylic acid or a phenol with a hydrocarbon-based solvent or a hydrocarbon-alcohol mixed solvent. For example, U.S. Pat.Nos. 2968642 and 2971014, 3147232,
The manufacturing method is known from No. 3533975, No. 4159973, No. 4252698 and the like. As such a complex,
For example overbased barium-2-ethylhexoate,
Overbased barium isodecanate, overbased barium oleate, overbased barium linoleate, overbased calcium isodecanate, overbased calcium oleate, overbased magnesium oleate and overbased barium dodecylphenolate-carbonate Overbased barium octylphenolate-carbonate, overbased calcium dodecylphenolate-carbonate, overbased calcium nonylphenolate-carbonate, overbased calcium thiobisdodecylphenolate-carbonate and overbased magnesium nonylphenolate -Carbonate complexes and the like. These alkaline earth metal overbased complexes can be easily produced, but commercially available complexes can also be used. These commercially available complexes include, for example, LD2105, LD2106, LZ2 manufactured by Lubrizol corp., USA.
116 can be mentioned.

When used in the present invention, the above-mentioned alkaline earth metal overbased complex is added in an amount of 0.1 to 4 parts by weight, more preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the base-containing resin.

Calcium hydroxide as the stabilizer component (b) of the present invention, when used in the present invention, is added in an amount of 100% chlorine-containing resin.
0.5 to 8 parts by weight, more preferably 1 to 5 parts by weight
Parts by weight.

Further, the zeolite used in the present invention have the general formula _{Na 2 O · Al 2 O 3} · pSiO 2 · rH 2 O below (in the formula, p is 0.5 ≦ p ≦ 3 and r represents 0.5 ≦ r ≦ 6.) a synthetic a type zeolite represented by, for example, _{Na 2 O · Al 2 O 3} · 2SiO 2 · 4.5H 2 O can be cited, and equiaxed a = 12.32A, other Na ₂ O · Al _{2
O 3 · 2SiO 2 · H 2} O, Na 2 O · Al 2 O 3 · 2SiO 2 · 0.5H 2 O and NaO · Al ₂
Examples include O ₃ .2SiO ₃ .4H ₂ O. The smaller the particle size of such a zeolite, the more advantageous it is in the present invention, and it is desirable that the average particle size is 10 microns or less, preferably 1 to 5 microns, and 90% or more. And
When used in the present invention, the addition amount is a chlorine-containing resin.
0.1 to 5 parts by weight, more preferably 0.5 to 100 parts by weight
~ 2 parts by weight.

The complex of the metal salt of perchloric acid of the stabilizer component (C) of the present invention with a polyhydric alcohol or its derivative is represented by the following general formula [Me
(ClO ₄ ) _n ] [R (OH) _x ] y (In the formula, Me is sodium, magnesium, calcium, or barium, n is a number of 1-2, x is a number of 1-3, and y is 1 And R are each a residue except a hydroxyl group of a polyhydric alcohol or a derivative thereof) and are liquid complexes at room temperature.

[Me (ClO ₄ ) _n ] constituting this complex is sodium perchlorate, magnesium perchlorate, calcium perchlorate or barium perchlorate. Further, in [R (OH) _x ] _y , R is a residue excluding a hydroxyl group of a polyhydric alcohol or a derivative thereof (hereinafter referred to as “glycols”). Examples of the glycols referred to here include ethylene glycol,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol, diethylene glycol monomethyl ether,
Diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, polyethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Mention may be made of propylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol, 1,4-butanediol, 1,5-pentadiol and glycerin.

Then, in order to form this complex, the reaction ratio of the metal salt of perchloric acid and glycols is 10:90 to 70:30 by weight ratio, preferably 20:80 to 55:45 by weight ratio. The complex having this specific ratio is a colorless to yellowish-brown liquid and is a transparent to translucent liquid at room temperature. When this complex is used in the present invention, the amount of addition is chlorine-containing resin.
0.2 to 5 parts by weight, more preferably 0.
5 to 2 parts by weight. As described above, the chlorine-containing resin composition of the present invention requires the addition of the three components of the above-mentioned stabilizer components (a) to (C) as an essential constituent element, and thermoforming is performed by this synergistic effect. It exhibits excellent effects not only in time but also in preventing thermal deterioration and coloration when exposed to a high temperature atmosphere for a long time, and also in workability such as plate-out.

The present invention also includes the following known stabilizers, stabilizing aids or other additives such as organic acid metal salts, organic metal salts, organic phosphites, antioxidants, β-diketone compounds, and inorganic compounds. Known compounds such as metal salt compounds and epoxy compounds can be used in combination.

Organic acid metal salts are commonly referred to as metallic soaps, the metal being sodium, potassium, magnesium, calcium, barium or zinc, and the organic acid binding to the metal being carboxylic acids or phenols. Examples of the carboxylic acid include hexanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, isodenoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, palmitoleic acid, oleic acid, ricinoleic acid, and linoleic acid. , Isostearic acid, 12-hydroxystearic acid, adipic acid, azelaic acid, sebacic acid, benzoic acid, toluic acid, xylic acid, pt-
Butyl benzoic acid, pt-octyl benzoic acid or mixed carboxylic acids thereof. Examples of phenols include pt-butylphenol, pt-octylphenol, nonylphenol, dinonylphenol, decylphenol and dodecylphenol. These organometallic salts are generally called nontoxic or low toxic metallic soaps.

The organic metal salt is represented by an organic tin compound, and examples thereof include dimethyltin bis (isooctyl glycolate) salt, dibutyltin laurate, dibutyltin arrayate polymer, dibutyltin bis (monoalkyl maleate C _{2 to} C _18). ) Salt, dibutyltin bis (isooctyl thioglycolate) salt, dibutyl tin thiopropionate, monooctyl tin tris (alkyl C ₁₂ -C ₁₄ thioglycolate) salt and dioctyl tin bis (isooctyl glycolate) salt And so on.

Representative compounds of the organic phosphite used in the present invention include triphenylphosphite, triisooctylphosphite, triisodecylphosphite, trisnonylphenylphosphite, diphenylisodecylphosphite, diphenyltridecyl. phosphite, distearyl pentaerythritol diphosphite, tri-2,4--t- butylphenyl phosphite, tetra-alkyl (C ₁₂ ~C ₁₅₎ -4,4'- isopropylidene diphenyl diphosphite, tetrakisphenyl Examples include dipropylene glycol diphosphite, tetrakisnonylphenyl dipropylene glycol diphosphite, and poly (dipropylene glycol) phenyl phosphite.

Further, as the antioxidant used in combination with the present invention, hindered phenols such as 2,6-di-t-butyl-4-
Methylphenol, 2-2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), and dialkyl which is a sulfur-containing alkanoic acid alkyl ester. Examples thereof include lauryl thiodipropionate and distearyl thiodipropionate. Examples of β-diketone compounds include benzoylacetone, dibenzoylmethane, myristoylbenzoylmethane, palmitoylbenzoylmethane, and stearoylbenzoylmethane.

Other stabilizing aids are epoxy compounds,
For example, epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxidized soybean oil fatty acid butyl, epoxidized linseed oil fatty acid butyl, ester of epoxy stearic acid with butyl or 2-ethylhexyl alcohol, bisphenol-A-diglycidyl Epoxy compounds such as ether, and as the inorganic compound, for example, magnesium oxide, calcium oxide, calcium phosphate,
Examples include aluminum hydroxide and synthetic hydrosaltite. Then, benzotriazole-based and hindered amine-based, which are light stabilizers, such as 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2-
(3,5-di-t-butyl-2-hydroxyphenyl)-
5-chlorobenzotriazole, dimethyl succinate-1
-(2-hydroxyethyl) -4-hydroxy-2,2,6,
Compounds such as 6-tetramethylpiperidine polycondensate. Further, an organic phosphorus compound as a processing aid, for example, nonylphenoxypolyethoxyphosphoric acid, tridecylhydroxypolyethoxyphosphoric acid and the like can be mentioned.

In the present invention, the above-mentioned stabilizers and stabilizing aids can be appropriately used for the purpose of further improving thermal stability, light (weather) resistance or processability.

Examples of the chlorine-containing resin in the present invention include polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-propylene copolymer, vinyl chloride-butanediene copolymer, vinyl chloride-urethane copolymer and polyvinyl chloride. And chlorinated polyethylene, chlorinated polypropylene,
Further, polyurethane and blended products with acrylonitrile-butanediene-styrene copolymer, methacrylic acid ester-butanediene-styrene copolymer or nitrile-butanediene copolymer can be mentioned.

The chlorine-containing resin composition of the present invention provides a wide range of molded products from semi-hard to soft by varying the compounding amount of a plasticizer such as trimellitic acid ester according to the use of the molded product. If necessary, a filler, a pigment, an antistatic agent, an antifogging agent, a flameproofing agent, an antifungal agent, a crosslinking agent,
A foaming agent or other auxiliaries can be appropriately used in combination.

Next, the present invention will be further described based on the following examples.
However, the present invention is in no way limited by these examples.

Synthesis Example 1 120 g (1 mol) of diethylene glycol monomethyl ether was heated while stirring, and when the temperature was 80 ° C., 112 g (0.8 mol) of sodium perchlorate (monohydrate) was added little by little and suspended in the glycol. Next, the temperature was gradually raised with stirring to dissolve at 100 ° C. Further, it was gradually heated to react with a mild exothermic reaction. 110
The water was distilled off under reduced pressure at ℃, and the calculated amount of water was removed. After the reaction was completed, a complex of 215 g of a yellow transparent liquid was obtained.

Synthesis Example 2 Using 115 g (0.6 mol) of tripropylene glycol and 112 g of sodium perchlorate (monohydrate) (the same salt as in Synthesis Example 1), the synthesis was carried out according to Synthesis Example 1 and the yield was 210 g of a pale yellow transparent liquid. A complex was obtained.

Synthesis Example 3 Using 138 g (1 mol) of ethylene glycol monophenyl ether and 138 g (0.5 mol) of magnesium perchlorate (trihydrate), the synthesis was carried out according to Synthesis Example 1 to obtain a yellow transparent liquid complex with a yield of 245 g. .

Synthetic Example 4 Synthesized according to Synthetic Example 1 using 129 g (1.1 mol) of ethylene glycol monobutyl ether and 138 g of magnesium perchlorate (the same salt as Synthetic Example 3) as glycols,
A yellow transparent liquid complex with a yield of 235 g was obtained.

Synthesis Example 5 Using 134 g (1 mol) of dipropylene glycol and 155 g (0.5 mol) of calcium perchlorate (tetrahydrate), according to Synthesis Example 1, a yellowish yellow transparent liquid complex was obtained in a yield of 250 g.

Synthesis Example 6 118 g (1 mol) of ethylene glycol monobutyl ether
And 117 g (0.3 mol) of barium perchlorate (trihydrate) were synthesized according to Synthesis Example 1 to obtain a yellowish yellow transparent liquid complex in a yield of 215 g.

An infrared absorption spectrum was measured using an infrared spectrophotometer for each of the stabilizer component (C) complexes of the present invention synthesized in Synthesis Examples 1 to 6. As a result, [Me (Cl
O ₄ ) _n ] is 1140-1060 cm ⁻¹ and 630 cm ⁻¹ , and [R (OH) _y ].
Showed characteristic absorption at 3600-3200 cm ^-1 .

Moreover, in order to examine the stability of the liquid complexes synthesized in Synthesis Examples 1 to 6, a risk evaluation test for unstable substances was conducted as follows. As a test method, Tadao Yoshida "Chemical Safety", 19
According to the test method of the risk assessment test of unstable substances based on 82, (a) Exothermic and stability tests by differential scanning calorimetry (DSC) were performed.

The test results show that the liquid complexes of Synthesis Examples 1 to 6 all have a temperature of 60.
Between -220 ° C, it did not show any behavior such as exotherm and was stable.

(B) The Dewar bottle test, more specifically, the constant temperature heat storage storage test was set at a temperature of 150 ° C., and exposed for 168 hours to observe the heat storage decomposability.

As a result, each complex did not show any behavior such as heat generation due to heat storage or thermal decomposition. From these test results, it was found that the synthesized complex had almost no risk of heat generation or thermal decomposition.

Examples 1 to 8 In order to examine the heat stabilizing effect and processability of the chlorine-containing resin composition to which the stabilizers (a) to (c) of the present invention were added, various tests were carried out using the following compounded compositions. I went.

Blended vinyl chloride resin (Note-1) 100 parts by weight Plasticizer (Note-2) 60〃 Epoxidized soybean oil 3〃 Organic phosphite (Note-3) 0.8〃 Stabilizer (Table 1) -Vinyl chloride resin (Note-4) 15 〃 Note-1 ZEON 103EP-8 manufactured by Nippon Zeon Co., Ltd., average degree of polymerization 800 Note-2 Kao Co., Ltd. vinylizer N-08 Trinormal Octyl trimellitate Note-3 Tetraalkyl (C _12-15) Buss phenol
A. Diphosphite Note-4 Fine powder for paste, particle size 200 mesh 90% or more, average degree of polymerization 850 (1) Preparation of powdered resin composition 2000g of vinyl chloride resin was charged into a Hensyl mixer with a capacity of 20L and the rotation speed was 1000 rpm. Set to. Next, the stabilizer was added in an amount according to the blending amount and mixed while heating.
When raised to 60 ° C., the epoxidized soybean oil and then the plasticizer were added sequentially and mixed with further heating. The temperature of the resin composition was raised to 120 ° C., and as it was, the mixture was mixed for 30 minutes to perform dry blending. After lining up, it was cooled with water. Fine powder PVC resin for paste at 40 ℃ 30
0 g was added and further mixed for 5 minutes to obtain a powdery vinyl chloride resin composition.

(2) Preparation of Sheet First, 200 g of the prepared powdery resin composition was prepared. Plate of nickel-chrome steel "size 300 x 300 mm, thickness 1.5 mm" heated in a gear oven set to a temperature of 240 ° C
Was taken out, and the resin composition was sprinkled on the mirror surface of this flat plate and left standing for 10 seconds for welding. Next, the unwelded resin composition was scraped off. This flat plate was again placed in a gear oven set at 240 ° C. for 50 seconds, melted and taken out, and then rapidly cooled to obtain a sheet having a diameter of 200 mm and a thickness of 0.75 mm.

The following tests were performed on this sheet.

Test-1 (a) A color oven due to heat deterioration and a black decomposition time were examined by putting the test piece in a gear oven aging tester heated to a temperature of 260 ° C. for a certain period of time.

(B) When the above sheet was sampled from a flat plate, the peelability of the sheet and the mold contamination (plate-out phenomenon) generated on the mirror surface were examined.

The results are shown in Table 2.

(3) Integral molding with urethane foam First, the sheet obtained by the above method (2) was set in a mold. Next, a polyol for urethane foam (EP-3033, manufactured by Mitsui Toatsu Chemicals, Inc.) and polyisocyanate (MDI-CR-200, manufactured by Mitsui Toatsu Chemicals, Inc.)
Stir at a weight ratio of 0: 7. This urethane undiluted solution was poured into a sheet set in a mold and foamed to obtain a 20 mm-thick integrally molded product composed of a vinyl chloride resin sheet and urethane foam.

The following tests were performed on this molded product.

Test-2 (a) This molded product was exposed for a long time in a gear oven aging tester heated to a temperature of 120 ° C., and the coloring state due to heat storage was examined.

(B) Molded products that have been exposed for a long time JIS-K-7113-81
A physical property test was performed based on the “Plastic tensile test method”.

The results are shown in Table 3.

Claims (1)

[Claims] 1. A chlorine-containing resin containing (a) an alkaline earth metal overbased carboxylate or phenolate complex as a stabilizer, (b) zeolite and calcium hydroxide, and (c) sodium perchlorate. A heat-stabilized chlorine-containing resin composition comprising a combination of a magnesium, calcium salt or barium salt and at least one complex of a polyhydric alcohol or its derivative.